The spectrophone method for the study of vibrational relaxation
has been claimed to possess a distinct advantage over the more commonly
used ultrasonic techniques in that it permits the relaxation of
the various infrared-active vibrational modes in a polyatomic molecule
to be studied separately. A discussion of the rate equations...
The silicate phases of 11 pallasites were analyzed instrumentally
to determine the concentrations of some major, minor, and
trace elements. The silicate phases were found to contain about
98% olivine with 1 to 2% accessory minerals such as lawrencite,
schreibersite, troilite, chromite, and farringtonite present. The
trace element concentrations, except...
Basalts of both Eocene and Miocene age from several groups
along the Oregon and Washington coasts have been analyzed for some
major, minor, and trace elements using instrumental neutron activation analysis (INAA). The rare earth element (REE) patterns observed
in these samples are used for comparisons within the groups studied...
Steroid carbenes have been investigated as synthetic intermediates.
Basic decomposition of 4-en-3-one tosylhydrazones (and
other A-ring systems) gives varying amounts of 2, 4-dienes, and
solvent derived products with diglyme, heptane, tetrachloroethylene,
carbon tetrachloride, benzene and cyclohexene. A method for
separating complex product mixtures was developed and a study of
the...
The 3-cyclohexenyl carbinyl carbene species was formed by the
thermal decomposition of the p-toluenesulfonylhydrazone sodium
salt and by oxidation of the hydrazone. Several oxidizing agents
were studied. The products were investigated under aprotic and
protic conditions and at various temperatures. The diazocompound
was formed as an intermediate and found to...
Graphite oxides which had been prepared from three different
size graphite particles by the modified Brodie method were observed
with the electron microscope. The thermal decomposition products
of the oxides, obtained by heating them at 240° and 300°,
were observed using the electron microscope and x-ray diffraction.
Graphite oxide was...
The Diels-Alder reaction represents a promising tool for use in
asymmetric synthesis. The reaction involves a rigid transition state
that facilitates the formation of one diastereomeric transition state
and is reversible. This satisfies two necessary criteria for
asymmetric synthesis.
The Diels-Alder reactions of 1,l-dialkylspiro[2.4]-4,6- heptadienes
with maleic anhydride and p-benzoquinone...
This dissertation is separated into two parts according to the two major distinct research projects. In Part I, the full account of synthetic studies toward C10-functionalized lycopodium alkaloids is described. In Part II, the detailed discussion on the exploration of the Pummerer cyclization methodology and its application to the total...
Bromoalkoxylation of dihydropyran with bromine and 1-borneol, followed by dehydrobromination and epoxidation, afforded trans-2-1- bornyloxy-3,4-epoxytetrahydropyran as a major product. This was treated with sodium phenylselenide to give a 1:1 mixture of (2R,3R,4R)- 2-1-bornyloxy-3-hydroxy-4-phenylselenotetrahydropyran and its (2S,3S, 4S) diastereomer. Elimination of the selenoxide, derived from oxidation of the former with hydrogen...
Perdeutero-spiropentane (C₅D₈) has been synthesized and infrared and Raman spectra are reported for the first time. Wavenumber assignments are made for most of the fundamental vibrational modes. Gas phase infrared spectra were recorded at a resolution (0.002 cm⁻¹) sufficient to resolve individual rovibrational lines and show evidence of strong Coriolis...
The tosylhydrazones of 2-heptanone, 4,4-dimethy1-2-
heptanone, 6-heptyn-2-one and 4,4-dimethy1-6-heptyn-2-
one were synthesized and decomposed under a variety of
reaction conditions: dry lithium and sodium salt pyrolyses,
sodium methoxide thermolyses in diglyme and photolyses of
the lithium salt in tetrahydrofuran. The saturated analogues
2-heptanone tosylhydrazone and its 4,4-dimethyl
isomer afforded the...
In situ, reduction of Cp*ReO₃ by PPh₃ to form (Cp*ReO)₂(μ-O)₂ allows catalytic deoxygenation of epoxides, however, conproportionation between Reⱽ and Reⱽᴵᴵ species to form clusters of ((Cp*Re)₃(μ-O)₆}²⁺(ReO₄⁻)2 and new compound {(Cp*Re)₃(μ²-O)₃(μ³-O⁾³ReO₃}⁺(ReO₄⁻) leads to removal of rhenium from the catalytic cycle and loss of activity, The epoxide deoxygenation mediated by (Cp*ReO)₂(μ-O)₂...
Lycopodium alkaloids have shown widespread and noteworthy biological activity, consisting of over 250 known natural products. Moreover, their structural complexity and diversity have attracted considerable attention from numerous laboratories including our own. Recently, we have developed a unified approach that would provides access to numerous, previously unprepared C₁₀-functionalized lycopodium alkaloids....
This thesis describes the development of a new enantioselective synthetic method employing chiral cis-2,5-diaminobicyclo[2.2.2]octane-based organometallic catalysts. The significance of this new method to organic synthesis is illustrated with preparation of enantioenriched products that are transformed to important pharmaceutical agents. Chapter 1 provides a brief historical overview of asymmetric catalysis, especially...
Contaminant transport in ground water is an important environmental process that
affects a host of natural systems. Transport of contaminants is affected by many
processes, including aqueous complexation, adsorption, and redox reactions. One of the
most important components of an aquifer that controls transport is iron-oxide. In this
study, the...
Studies toward the total syntheses of highly potent cytotoxic alkaloids
including the bromopyrrole alkaloids and indole alkaloids were conducted and are
described. Studies carried out in the course of this dissertation consist of five total syntheses of natural products that include bromopyrrole alkaloids nagelamide A, D and agelastatin D as...
Metal-organic polyhedra (MOPs) are discrete molecules comprised of a metal and interconnecting ligands. The resulting MOP structures are porous cages, and to date, they have shown great promise toward gas capture. Ammonia is a hazardous gas that is produced in enormous quantities for use in fertilizers. In this talk, I...
Inorganic structures play an important role in materials due to their versatility and diversity. A complete understanding of the structure of a material is vital to enhance the creation of new materials that fill voids in research. The rational design of these compounds is driven by the exploitation of structure-property...
The velocity of sound in gases was measured, using an ultrasonic
wave train as a diffraction grating. The fundamental problems
involved in the optical technique are discussed. An apparatus utilizing
an objective lens of focal length 1.5 m and aperture f/20 was constructed
and used at an ultrasonic frequency close...
The electrochemistry of cadmium at a Reticulated Vitreous
Carbon (RVC) electrode has been studied to determine the suitability of
RVC as a working electrode for the electrochemical preconcentration of
cadmium in the corrosive environment of zirconium dissolved in
hydrofluoric acid.
The electrochemistry in this investigation deals with deposition
of solid...
Many D2d-symmetric 2,2',6,6'-tetrasubstituted biphenyls are
readily prepared via net oxidative dimerization of appropriate
1,3-disubstituted benzenes. Conversion of such proprochiral
compounds to useful C2-symmetric chiral biphenyls requires
formal replacement of two substituents on opposing aryl ring
units with alternate groups. This under exploited
desymmetrization tactic has been demonstrated for the
generation...
The tosylhydrazones of exo-3-deuteriocamphor and 2- deuterio-2,4-dimethy1-3-pentanone were treated with Nbromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at. C[subscript...
At Site-300, Lawrence Livermore National Laboratory (LLNL), CA,
trichloroethene (TCE) is present along with tetraalkoxysilanes such as tetrabutoxysilane
(TBOS) and tetrakis(2-ethylbutoxy) silane (TKEBS), as subsurface contaminants.
Intrinsic transformation of TCE to cis-dichloroethene (c-DCE) was observed in the
groundwater at locations co-contaminated with TBOS or TKEBS. Attenuation of TBOS
and TKEBS...
The distribution of hydrophobic ionogenic organic compounds
(HIOC's) between aqueous and nonaqueous phases has been
investigated. The HIOC's are aniline and methyl substituted
anilines. The aqueous phases are methanol-water mixed solvents with
varying pH and ionic strength. The nonaqueous phases are silica and
alkyl derivatized silica with ethyl- (C-2), octyl-...
We report the use of MIL-120 as a water-stable and cost-effective metal-organic framework (MOF) for selectively capturing CO₂ from wet flue gas. Synthesized using inexpensive and environmentally benign reagents in water, MIL-120 possesses one-dimensional pores decorated with hydroxyl-bridged Al(III) ions and benzene rings with an interstitial spacing of 4.78 Å....